7

Non-ideal solutions

The concept
of activity
7.1
the equation 4; ( ) + RTIn (Section
=
x,
For many real solutions .1) does
the solvent, and the expression
which corresponds to OS
not hold for
6.10), 4, 4S)+ RTinx, also fails to hold for
=
Henry's
the sol.ys
Law (Section
Such circumstances it is convenient to introduce the concept of actinit
We
may wite

A +RTIna.
This equation defines the activity 4 of component i in terms of its chemical
potential in the solution and in the standard state. This activity may be
regarded as the effective concentration of component i relative to its standard
state. (Activity is defined only in so far as the standard state to which it relers
is also specified.) The effective concentration may, in a real solution, difer
greatly from the true concentration as a result of the interactions between the
molecules. The extent to which this is so is measured by the activity coefficient

Effective concentration
Real concentration

This can be illustrated by consideration of a real liquid mixture.

Figure 7.1 shows the vapour pressure of a solution in which the vapour
pressures of the components are said to deviate negatively from Raoult's Law

uncir vapour pressures are less than those predicted by the law). Writing the
cquations for the chemical potential of one component both in the soluuon
and in the
vapour phase,
HB)= H(g) + RTIn(P,/atm) (Section 4.10),
4,(soln) =
u) + RTln a.
Now
) (g)+ RTIn(P? /atm) (Section 6.1),
as the
pure liquid i must ated
be in equilibrium with its vapour at u*
 Vapour pressure/mm Hg

09

2.
 106 Non-ideal solutions

340 One phase

330
Two phases

320

0 20 40 60
Percentage phenol
Fig. 7.2. Partial miscibility of phenol-water mixtures as a function of temnerai, .
ature.

strongly from Raoult's Law in a positive manner, and separates into twa
phases as illustrated in Fig. 7.2.

7.2 Activity of solids in

liquids
When we looked at the solubility of naphthalene in various solvents
(Section
6.4), we found that in benzene the actual solubility was close to the truly ideal
value, as predicted on the basis of Raoult's Law, but in both hexane and
methanol it was considerably lower. The chemical
solute (and hence its activity in the solid
potential of the solid
the activity of the
state) is the same in all cases,
naphthalene solution must also be identical, for at
in
equilibrium
s ) = u(soln) = u°() + RTIn a.

Nevertheless the concentrations are

coefficients must vary. In the ideal casedifferent,
and therefore the act1vity

(soln) =
°() + RTIn xid
thus
x
a =
and y =
1. For the solutions which deviate from
Xid/x. ideality y a/x
=

Thus for hexane

y 0.30/0.12 2.5. The activity coefficient
unity indicates that a smaller
=
=

quantity of greater than

for it to attain the naphthalene
chemical potential of solid in solution is
necessary
were truly ideal.
We could
say that as the
naphthalene than if the solution
the solution' its
tendency to naphthalene 'does not like
stay in the solid state is being in
greater.
 Activity in aqueous
have tackled the
solutions 107
coula
could
problem in another
activity of theate naphthalene using the
We
way. If we defined
6.10) would obtain
Henry's Law standard state the
(from
Section we
?
+ RTIn a
Would not have the same value as
that
based
which has chemical potential on the pure-liauid
standard state,
iffcrent from system to .Unlike . uwoul be
system so that a ditterent
htained for naphthalene in dinerent solvents. The use of thisvalue would be
will be discussed in the next sectioon. standard state
Ac naphthalene in hexane follows Henry's Law
(but not Raoult's Law) the
activitycoeficient defined on this basis would be
cquation approximately
4+ RT Inx, holds for this system. Whether
= unity, as the

or the Henry's Law standard state is used in

the pure-liquid
any thermodynamic
is purely a matter of convenience. There
is no calculation
objection fundamental thermodynamic
to using
any standard state. In the
considering it is sometimes helplul to have the particular problems we are
unity so we can apply the equation 4, activity coefficient cqual to
u° =
+ RTInx, to the
the varying behaviour of system.
other hand, if we wish to On the
quantify
ifferent solvents the
activity coefficients based
naphthalene in
on the
state give us a convenient measure.
pure-liquid standard

7.3 Activity in
aqueous solutions
Many chemical experiments are carried out in
important to be able aqueous solutions and it is
to define activities in these
Standard state we have used so far
circumstances. However, the
-the
pure liquid at one atmosphere
pressure-is
ons in
singularly inappropriate. We usually wish to
molality (moles per express concentra
a SOdium chloride, the kilogram solvent) and for
of
electrolyte, such
an
pure-liquid state at room
suitable reference state. temperature S not a
tne solute follows Henry's Law (Section 6.10),
dy the case when the solution is very dilute and4, we u? + asRT|ln x,. This
=

previous section, define may, indicated in

an
activity such that
and H +RTln a, 4 + RTln x,y. =

nder these circumstances

the solute
to its t a X as x, > 0. To refer the properties of
Concende.
relerene behaviour at nfinite dilution clearly gives a more reasonable
The actual reference state is in fact a solution for which the
erm x
dilute solution, is unity and whose properties are those of an inhnitely
to use! for wh
which y = 1. This concept is more difficult to grasp than
We illustrate the
pure liquid (x standard state diagrammatically in Fig. 7.3. It is a
)with a
vapour pressure Pe and a chemical potential4?.
 108 Non-ideal solutions

P Standard state p

Henry's Law

0 mole fraction x,

Fig. 7.3. Definition of a standard state for a solute, based on Henry's Law

For an electrolyte solution the procedure is similar but we use

unit
molality, m, = I mol kg,as the concentration of the standard state. Then
for an ideal solution

+ RTIn m
H mol kg T
and for a non-ideal solution

i 4 + RTln a

+ R7Tln m
mol kg
Now 4 is the chemical potential of an ion in a (hypothetical) solution of unit
molality which behaves like a solution of infinite dilution (where , = 1,
I mol
m, =

kg"', and 4 =

H).
Including the dimensions of molality makes the resulting equations clumsy
and for this chapter we will adopt a simplifying convention that takes m to

represent molality/mol kg'. Thus m now represents a dimensionless ratio

equal to the number of moles of solute per kilogram of solvent.
The equation

+RTin a
must be modified when we apply the concept of activity to the electrolyteasa
au Cnioride is essentially fully dissociated (NaCl Na" +C
 Activity in
aqueous solutions 109
Lation, We can only deal with the
in aqueous so,
overall activity
in
of determining aNa. and aNaci as we
haveno way
would
a independently. As each of the
have nobeexpected to follow Henry's Law independently, the total chemical
ions
can be written
potential
Htotal4Na + &- + RT In ana t+ RT Inac
If we define the overall activity by the equation
otalNa +-+ RT In aNaCI
by compar1ng these equations that
we can see

aNaCIaNa .Gci
and
aNaCI ?Na mNa .Vci- mcI
ma mcI = m the molality of the solution.
We can define a mean 1onic
activity coefticient y+ by
Y(7NaVc-)
Then
aNaCI(7+m)*.
Indilute solutions, where y, 1 , aNacI will be directly proportional to m.
This is illustrated in Fig. 7.4. When the
electrolyte is more complex the
definition of overall activity must be modified accordingly:
for M,A,pM* + qA. aMpAg(aM.(a -)
and
P+ =
(M P(yA-Y.

NaCI

Standard state
1-0

10
m2
Fig.7.4 Detinitie of a standard state for a 1:1 electrolyte based on Henry's Law
n
 110 Non-ideal solutions
different from those
Remember, both y, and a, are based
apure-li
standard state. The relerence state has changed and a, and
are
relative to that state. Strictly, in order to define the different activities
pure-liqui
three cquations
defined
should write the we

(x, =
1)+ RTin a, (see Section 7.1)
A =

)+ RTIn a,,
4=°(x,
=

and
1) + RTIn a.
4S (m,
=

4 =

In the examples that

follow we shall always use the definition of activity
as the standard state.
based on unit molality

7.4 Chemical equilibria in solution

We have previously considered equilibria between pertect gases in which the
chemical potential of each component followed the equation derived in
Section 4.10:

H(B)= g)+ RTIn(P./atm).

In solution we may write for the chemical potential u, = 4 + RT In .

(Section 7.2), where the standard state is one of unit molality which behaves
as if it were at infinite dilution. Let us consider the simplified equilibrium

AB

mA
HA = # + RTin a = + RTln 7A mA

HB + RTIn ag = / f + RTIn 7p/mg.

At equilibrium PA PB and AG =4 - #R = - RTin ag/4=

- RTin K

AG is the change in free energy when a mole of A at unit molalityy is

transformed into a mole of B at the same concentration, both solutions
behaving as if they were at infinite dilution. In other words the free-energy
change for one mole of reaction with both reactants in their standard states
AG RT In K,. K,, the equilibrium constant expressed in terms olis
activities, is exactly constant at any given temperature and pressure. As

K = 9M BK
VA mA A
where K, is the
not an equilibrium constant expressed in terms of
exact constant
and is equal to molalities. This is
both reactants
and products K, only when y 7a 1, that is when = =

follow Henry's Law.

Again it must be re
 Chemical equilibria in solution | 111
membered that a AG° and K,, like a, and y,,
depend on the choice of standard
state.
a alutions, as for gases, we may calculate the
fK, using the Vant Hon Isochore (Section 4.12).
temperature dependence

InK.]
OT "
AH
RT?
JHe is the difference in enthalpy between the products and reactants in
their
ctandard states for one mole of reaction. For systems not at equilibrium the
hange in free energy for a mole of reaction, all concentrations being
maintained constant is, as before,

AG' AG° + RTIn

ag/a^
=

AG, the so-called reaction free energy, is (OG where is the extent of
reaction (Section 4.11).
An important case of equilibrium in ionic solutions is the
sparingly soluble salt, for example, silver chloride solubility of a

AgCls) Ag* (aq) + CI (aq).

The chemical potential of the solid is constant, thus we obtain

HAgcilS)= g + RTn aag. + - +

RTIn ac
and

RT(ln aAg + +In ac-) = const

or

Ag.C = K,.

he constant K, is known as the solubility product of the salt:

K, =

('As Yc )mAmer
n e salt Is only slightly soluble the activity coefficients will be close to unity,
thus

K, = mAg Mc m

Owever, if we dissolve the salt in an electrolyte solution (with no 1on in

on we find that the activity coefficients are usually less than unity and
as
K, = Yc m is a constant, m2 is greater than its value at infinite
dilutior n (AsY
other words the presence of the other ions in solution tends to
Crease solubility of the sparingly soluble salt.
the
uswe find that the solubility of thallium (I) chloride TICI is 0.016
mol k in distilled water and
0.023 mol kg"' in a 0.30 mol kg"' soluti0n
112 Non-ideal solutions

be calculated that the mean activit.

of KNO. It can
ivity coefficient of thethe salt
(T Yc-) sa
in pure water is 0.88. When TICI
dissolved is dissolved in
KNO, the mean activity ity
coetficient is 0.61. 0.30 mol
water is sufficient to cause coralionficient
We note that the ionic concentration produced by TICl
the activity coefficient to
to
TICI w
when it dissol.
unity, its value at infinite dilution. A lamous theory due to De
provides the explanation lor this interesting behaviour.t
kg
depart
gnifidicandantssollyvHück
siDebye
and Hückel
esftomi
ückel

7.5 Electrochemical cells

The systems we have studied so far have not been harnessed
have only done work by expanding agains tod work
these conditions the position of
atmospheric an
pressure Und
equilibrium is defined by the eauot
derived in Section 4.2: tion
dG =0 (T, P const).
However, the electrochemical cell is one important chemical
work other than PV work is system in which
the appropriate performed. In this situation dG
equilibrium condition. In such a cell when the dwadditinat is
=

is open the electrodes will external circuit

have different clectrical
from the tendency of the
electrode material to potentials. These will arise
into solution as ions give up electrons and to
(or vice versa). On pass
chemical reactions take connecting the external
circuit,
one electrode place which lead to electrons
and transferred to the
other. If an electric
being removed from
flow through an current is allowed to
external
gradient, it can be used to circuit, linking the electrodes
down the
A simple cell is illustrated
do work. potential
in
Fig. 7.5. One electrode is
surrounded by a solution of a
in a solution
of a
zinc salt, the other is made of made of zinc
1ons can flow copper salt. The solutions copper immersed
from one can be linked
in such a
bridge', is arranged so compartment
as to
to the
other, but the connection,way that
tendency in such a cell is for prevent the solutions a 'salt

making the zinc electrode the zinc to form ions and mixing too rapidly. The
end to to give
gain electrons andnegative. Conversely,
the
up electrons
reaction is be copper ions in
deposited as metallic solution
copper. The overall
Zn +Cu* - Cu
n the external circuit + Zn**.
from the the flow of
negative zinc. electrons is to the
tSee Atkins positive copper
Physical electroule
chemistry, fourth edition, (Chantu
 Electrochemical cells| 113

Zn Cu
inert electrolyte

Zn +* Cu

Zn Zn **
+ 2e C u + 2e » Cu
Fig. 7.5. A simple electrochemical cell.

The maximum electrical work done by such a cell is equal to the product of
charge flowing and the potential difference across which it flows. The
work done on the cell is

W - EQ (see Section 2.1),

where E is the electromotive force of the cell and Q the charge flowing. For
one mole of the
cell reaction

nNAe
GTE NA is Avogadro's number, - e is the charge on the electron and n is
m b e r of moles of electrons transferred per mole of reaction. The
Prauct NAe, the magnitude of the total charge of a mole of electrons, 1s
caled the Faraday and written F. Thus
W - nFE.
For thedction
reacti we have considered, two electrons are transferred from the
zinc to the
nfinitely
If the cell copPP for under
sorked reversible
a mole
conditions
of reaction and so (that
n is,2. the current is drawn
=

infinitely slowlyt) then

accordingly we may regard the system as in equilibrium, and

For oneO C dWadditional (T, P const) (Section 4.2).

of
the cell reaction under constant conditions we may write

AG = nFE
tTo do this
* a l C.m.f. must be applied to balance the e.m.f. of the cell
 114 Non-ideal solutions

where AG' is the reaction free energy. (If the reaction were
significant extent the concentrations of the electrolytes w

before AG is therefore strictly the differential term(

/T,P
where isthe
extent of the reaction. See Section 4.11.)

As we can write for a simplified cell reaction (see Section 741

AB

AG =
AG° + RTln(a,/a^).
SO
nFE = -

nFE° + RTIn(ag/a),
or
E =E° -

(RT/nF) In (a,/a,).
For a more general cell reaction

aA + hB/L + mM
we would obtain

E =E° (RT/nF) In (afam/aag).

This equation is the Nernst
equation which relates the e.m.f. E of a cell to
E, the e.m.f. of the cell when all the
reactants and products are in their
standard states. E° is called the standard
If the composition of the e.mf. of the cell.
electrolyte solutions is such that the
is at
equilibrium, there is no tendency for current to flow and the cell reaction
e.m.f. of the
cell will be zero. Then

E 0 and RT
E°=InK,.
n ink,,

where K, is the
other equilibrium constant of the cell reaction. The
thermodynamic quantities can be obtained
AG =- nFE.
changes in
from the equation
As

as = (AG)]
(Section 4.4),
s -(7
and

AH' =
AG' + TAS' =
nFE +| (OE
0TnFT
 Standard electrode potentials 115
|
h ep r i m e s
te that the AH' and AS' reler to a mole of reaction carried
i n d i c a t e

substances participating in the cell reaction maintained at a

The

o u t

ncentration. H is equal to the heat absorbed at constant

w i t h

ifed nly if no work, other than P work, is done. In an electro-

p r e s s u r e( q ) , o n l
syecn

aand the hcat of reaction is not AH'. We

work is done may
chemical cell from the
the relation AS = 4./T which gives the reversible heat
from
culate(9),
(9), TAS'
=

as
The
absorption chemical cell
rochemical cell provides a very powerful way of determining
stants and the changes in thermodynamic properties accom
quilib in solution.1
reactions

Oanying

Example

e.m.f. of the cell

The

AglAgCls)HCl{aq)}Hg,Cl,|Hg
AQ471 V at 288 K and 0.0489 V at 308 K. Use this information to estimate AG, AS,
is 0.0
the cell reaction
and AH for
2Ag + Hg,CI, 2AgCl + 2Hg at 298 K.

The value of the e.m.f. at 298 K is taken as the mean of the values given, that is
0.0455 V. Then

AG - nFE = - 2 x 96 500 x 0.0455 J mol

8.78 kJmol

0.0489 0.0421\
AS = n A T = 2 x 96500
20 K'mol
65.6J K'mol
AH AG + TAS = 10.76 kJ mol".

The negative value of AG results from the favourable entropy change that accom
panies the reaction.

7.6 Standard electrode

potentials
we could measure the tendency ofeach possiblehalf of an electrochemical
C cach electrode and the solution in which it is immersed) to take up or
eicase electrons, then we could calculate the e.m.f. of a cell made up of two
uCn clectrodes. We cannot measure this tendency on an absolute basis but it

n general background to electrochemistry will be found in Atkins Physical chemistry.

edition (Chapter 10) and the way electrochemical properties affect the inorganic properties
1Ons is described in G. Pass's lons in solution (3): Inorganic properties (OCS7)
 116 Non-ideal solutions

Pt M
Salt bridge

M' (a = 1)
H (a =
1)
a hydrogen electrode set up to determine
Electrochemical cell ith
Fia. 7.6.
e l e c t r o d e potential
of element M.

is sufficient if we can measure it relative to some reference electrode The

standard hydrogen electrode which is assigned th
standard chosen is the
at 1 atm intocontact with
value E 0. It is made by bringing hydrogen gas
a solution of its
ions at unit activity at the surlace of a platinum electrode
electrode potential of an element M we set un a
To determine the standard
cell as illustrated in Fig. 7.6. The element is placed in a solution of its ions at
unit activity (standard state, based on the unit-molality definition) and
The potential of element M with
coupled to a standard hydrogen electrode.f
electrode is called the standard
respect to the platinum of the hydrogen
electrode potential of M. (If the element M is positive with respect to the
hydrogen electrode then the standard electrode potential of M is positive and
vice versa.) If the metal in the cell is zinc we find

E°(Zn* *,Zn) =- 0.76 V.

For copper
E°(Cu*, Cu) = +0.34 V.

As zinc electrode tends to dissolve,

a
forming zinc ions, the electrode tends to
become negative, and in effect withdraws electrons from the solution:
Zn Zn**+2e.
On the other hand
the copper electrode tends to lose electrons, becoming
T
In practice we do not
try make up solutions of unit
to
knowledgeinof the activity coefficients activity-this would require a
solutions the cell so that the of the ions in solution. Instead we can use
calculated using the Nernst activity coefficients are very diu
of the ions. equation (Section 7.5), essentially unity. E can
then De
replacing the activities by the
concentrations
 Standard electrode potentials
| 117
-0-76V w i t h r e s p e c t
+0.34V with respect
to H*, H2
to H*, H
Zn Cu

Zn (a = 1) Cu++(a = 1)

Cut, Cu -+0-34

Standard
hydrogen 0-0
electrode e.m.f. of cell

Z n , Zn -0-76

Determination of the standard e.m.f. of a cell from the standard electrode

Fig. 7.7.
potentials of the component half-cells.

positive. At this electrode the reaction must be

Cut + 2e Cu.
The e.m.f. of a cell with zinc and copper electrodes as in Fig. 7.7 can be
calculated from a knowledge of the standard electrode potentials of these
The standard e.m.f. of the cell is the difference between the standard
iements.
electrode potentials:
E°= Eh.s. - EShs, = 0.34 - ( -0.76) = + 1.10 V.

We conventionally record the e.m.f.s of cells as the potential ditlerence

Wen the right and the left electrodes. Thus if we had reversed the cell, so
T n was on the right, the sign of Ee would be reversed.
S t a n d a r d electrode potential of an electrode is a measure ol is
ele t o gain electrons. If Ee is positive the electrode will tend to gain
tends 1E° is negative the electrode will tend to lose electrons. Both these
the
most n are
measured The alkali metals have
relative to hydrogen.
* V electrode potentials whereas the halogen electrodes are very
 +
+ +

1 L
1 1
 Standard electrode potentials 119

Those elements with negative electrode potentials

sulphate solution.
c o p p e rs u l p h a
ner
similar way,
able to splace hydrogen from acids:
a
are
Zn + 2HCl » H, + ZnCl,

become passive like aluminium).

(unless they
(unless
the Nernst equationt
to a half-cell, for example a metal in
apply
We can
a solution
containing its ions
contact
with

E =E-RFa
reduced states. In the
of the oxidized and
the activities
and ag are
a the electrode
where
as Zn and
Cu one of the states is simply
such
solution containing both Fe2
of metals and
case not be so. If a
This need
material itself. platinum electrode, an
contact with an unreactive
into
Fe3+ ions is brought reaction
e.m.f. is set up
owing to the
Fe +e=Fe3*.
a standard
electrode (relative to
to this
may be applied
The Nernst equation
as before:
electrode)
hydrogen
RT aFe
E = E°
aFe
E° is found to
be +0.77 V.
In this case

Problems 21.8 and 23.8 mm Hg

at 298 K are
and water
0.20 their partia
n e vapour pressures of n-propanol mole fraction of
water is
activities
and

In a solution
in which the Calculate
the
Cpectively. spectively.

17.8 and 13.4 mm Hg in this

solution.
that of
pressures are
0.76 V, and
Zn), is
components
K
-

of the two at 298

activity coefficients ofzinc,E°
(Zn**,
otential
c o n s t a n t

The standard electrode

+0.34 V.
theequilibrium Estimate
V and
Copper, E (Cu *,Cu), is Zn=Cu + Zn E°(Ag.A
is 0.80
V.
Cu*+ is 0.22
Orthe reaction electrode
potential of silver,Pt(H,}HC|JAgCAg
electrode

At 298 K the standard cell (The

potential
of the temperature.

the standard electrode

of AgCl
at this
+
CI)
roduct Ag
lculate
»

the solubility + e
is AgCUs)
electrode

Ag
ction at the AgC1, Ag
the reaction
Ciectrochemical cell
in which
+ 2Ag(s) 273 K.
2AgCl{s)
- ZnCl,(aq) 1.015 V at
one
Zn(s)+ and
298 K accompanying

V at
1.055 enthalpy
of
and the
e.m.f.
Occurs has a standard
Gibbs free
energy
a
Estimate the changes in
nole of the cell reaction at 298 K.